Process for the dyeing of mixtures of cellulose, polyester and polyacrylonitrile fibers from one bath

ABSTRACT

Process for the dyeing of mixtures of cellulose, linear polyester and polyacrylonitrile fibers with reactive dyestuffs of the vinylsulfone type, disperse and cationic dyestuffs, wherein the goods are treated with a bath containing alkalies, non-ionic dispersing agents, a reactive dyestuff and a disperse dyestuff at 20* to 80*C and wherein subsequently free acid and a cationic dyestuff are added and the dyeing is completed in an acid medium at 95* to 130*C. Compared with the hitherto used two- or threebath processes the process of the invention has the particular advantage of saving 25 to 50 percent of dyeing time.

United States Patent; 1191, 1111 3,807,945

Von der Eltz et al. Apr. 30,1974

[ PROCESS FOR THE DYEING OF MIXTURES OTHER PUBLICATIONS OF CELLULOSE, POLYESTER AND DuPont, Textile Flbers Technical Bulletin, Multifiber POLYACRYLONITRILE FIBERS FROM ONE Bulletin x413, Oct. 1959, 3 p g BATH DuPont Technical Information, Orlon Acrylic Fibers, [751 Inventors: Hans-Ulrich Von der Eltz, Bull tin OR-171, June 1970.

Frankfurt/Main; Jmalmes Jethss Fortess et al., American Dyestufi Rep., May 27, 1963, Weiskirchen, both of Germany pages 16 25 [73] Assigneez Farbwerk Hoechst Keaton et al., J. Soc. Dyers and Col., Vol. 80, pages Aktiengesellschaft Vormals Meister June 1964- Kucius & Bruning, Frankf rt/Mai Man-Made Textiles, May 1958, page 64. Germany -Wygand, American Dyestuff Rep., pages 106-108.

[22] Flled: Jan. 1972 Primary Examiner-Herbert B. Guynn PP 220,469 Assistant Examiner Bruce H. Hess Related Us ApplicationvDam Attorney, Agent, or FirmCurtis, Morris & Safford [63] glpsrtggilzlton of Ser. No. 864,547, Oct. 7, 1969, [57] ABSTRACT Process for the dyeing of mixtures of cellulose, linear [30] Foreign Application Priority Data polyester and polyacrylonitrile fibers with reactive Oct. 8, 1968' Germany 1801715 dyestuffs f the tinylsulfone yp disperse and 1 ionic' dyestuffs; wherein the goods are treated with a [52] US. Cl; 8/21 C, 8/21 R, 8/21 A, i h containing alkalies, non-ionic dispersing agents, a g/2 reactive dyestuff and a disperse dyestuff at 20 to C [51] Int. Cl D06p 3/82 and wherein subsequently free acid and a Cationic 58 Field of Search 8/21 R, 21 A, 21 c, 177, dyestuff are added and the ye is completed in an /1 3 25 2 acid medium at to C. Compared with the hitherto' used twoor three-bath processes the process of l 56] References Cited the invention has the particular advantage of saving 25 3,199,942 8/1965 1411111 et al. 21/21 A 12 Claim No Drawings PROCESS FOR THE DYEING OF MIXTURES OF CELLULOSE, POLYESTER AND POLYACRYLONITRILE FIBERS FROM ONE BATH onitrile fibers from one bath with reactive, dispersion and cationic dyestuffs is connected with difficulties. These difficulties are due to the different dyeing conditions which are required for each of the three dyestuff classes.

Dispersion and-cationic dyestuffs in generalrequire long dyeing times and the use of dyeing temperatures of above 95 C. For dyeing, dispersion dyestuffs are applied as far as possible from an acid medium, because in the alkaline range the stability of the dyestuff dispersions is partly too low and, in addition, because some of the dyestuffs undergo, owing' to their sensitivity to alkalis, chemical modifications, especially at high temperatures, which entail changes in shade, losses of color yield and impairment of the fastness properties of the dyeings.

Cationic dyestuffs are also applied from an acid medium for dyeing, because in the alkaline range some of these dyestuffs tend to cause precipitations and to produce changes in shades and to impair the fastness properties of the dyeings.

Furthermore, cationic dyestuffs may form with the anionic reactive dyestuffs and some dispersion dyestuffs which contain polar groups an addition compound which may provoke precipitation of the dyestuff and deteriorate the fastness to rubbing of the dyeings'.

Reactive dyestuffs'require alkaline conditions to enable the reaction with the hydroxyl groups of'the cellulose fibers. With too long a dyeing time, however, especially at temperatures exceeding 95 C, the dyestufffiber bond is split by the action of the alkalis, which entails reduction of the color yield on the goods.

Now, we have found that the above-described disadvantages can be avoided and-that mixtures of cellulose, linear polyester and polyacrylonitrile fibers can be dyed from one bath with reactive, dispersion and cat.- ionic dyestuffs, by treating the said materials in the same bath, at first at temperatures in the range of from about C to 80 C with an aqueous bath which contains, in addition to the reactive dyestuff and the dispersion dyestuff, alkalis and non-ionic dispersing agents and, after addition of free acid and the cationic dyestuff, completing the dyeing in an acid medium, in general in a pH-range of from 3.5 to 6, at temperatures in the range of from about 95 C to 130 C.

The process of the invention permits adjusting. the pH-values of the dyebath in such a manner that they correspond to the respective fixing conditions of the reactive, dispersion and cationic dyestuffs without the need to use separate baths. It is extraordinarily surprising that, at the high temperatures used in an acid medium, hydrolysis of the bond between reactive dyestuff and fiber and therewith a loss of color yield do not occur. In addition, the, electrolyte quantities required for the dyeing of reactive dyestuffs on cellulose fibers and the reactive dyestuffs which remain in the bath and are not fixed on the cellulose fibers act as retarders for the cationic dyestuffs used for the dyeing of the polyacrylonitrile fibers. Thus, the application of the usual retarders used in the dyeing of polyacrylonitrile fibers with cationic dyestuffs is not necessary. By the simultaneous use of a non-ionic dispersing agent on the basis of oxalkylates and/or polyglycols, the water-insoluble addi tion compounds of cationic dyestuffs and anionic reactive or dispersion dyestuffs that contain polar groups can be kept in a fine dispersion so that precipitations and deteriorations of thefastness to rubbing of the dyeings are avoided.

For carrying out the process of the present invention, the textile material is treated for 10 to 90 minutes, preferably for 20 to minutes, with the bath which has been pre-heated to about 20 C, preferably to about 40 60 C, and which contains the non-ionic dispersing agent, the dissolved reactive dyestuff, the dispersion dyestuff and the agent having an alkaline action, during which time the reactive dyestuff is first fixed onto the cellulose fiber. Then, the cationic dyestuff which has been dissolved with free acid and hot water is added. Thereby, the pH-value is adjusted to a value in the range of from 3.5 to 6, preferably to 4.5 to 5.5.

The dyebath is then heated to a temperature in the range of from to C and the goods are left at this temperature for 30 minutes to 3 hours, preferably 45 to 90 minutes. During this time, the dispersion dyestuff is fixed onto the polyester fiber and the cationic dyestuff is fixed on the polyacrylonitrile fiber. It is of advantage for the fixation of the dispersion dyestuff on the polyester fiber to add a carrier to the dyebath after acidification. However, it is also possible to add the carrier already to the alkaline bath. After the dyeing, the goods are rinsed and soaped and treated in the usual manner.

Over the hitherto used twoor three-bath processes, the process of the invention for the dyeing of mixtures of cellulose, polyacrylonitrile and linear polyester fi bers from one bath has the particular advantage of a 25 to 50 saving of dyeing time. The process has another advantage when used in the dyeing with programcontrolled dyeing apparatuses. After charging of the dyeing apparatus and introduction of the cationic dyestuff dissolved with acid and hot water into the supplementary tank connected to the dyeing apparatus, the dyeing program can proceed automatically, without it being necessary to employ an operator. In contradistinction thereto, in the conventional twoor three-bath processes the dyeing apparatus has to be charged two or three times. I

As reactive dyestuffs, there may be used for carrying out the process of the invention those organic dyestuffs which contain as reactive component at least one vinylsulfonyl group or at least one group which forms a vinyl-sulfonyl group upon the action of the alkaline agents during dyeing.

As reactive dyestuffs, there are especially suitable those of the series of the anthraquinone, azo and phthalocyanine dyestuffs; the azo and phthalocyanine dyestuffs maybe metal-free or metalliferous. Of the class of groupings which can be converted during the treatment with alkaline agents into a vinyl-sulfone group which is capable of reacting with the cellulose fiber, there may be mentioned, as examples, in particular the sulfuric acid esters and thiosulfuric acid esters of B-hydroxy-ethyl-sulfone groups. Such reactive dyestuffs are disclosed in, for example, US. Pat. Nos. 2,670,265, 2,657,205, 3,197,456, 3,261,823 and 3,324,151.

As dispersion dyestuffs, there may be used according to the process of the invention the dyestuffs generally known in the dyeing of fibrous materials of linear polyesters, for example those of the series of the azo or anthraquinone dyestuffs. Such dispersion dyestuffs are disclosed in, for example, Color Index, 2d Ed., 1956, Vol. 1, pp. l659l742; 1963 Supplement, pp. 5179-8224; and Additions and Amendments, N0. 1, Sept. 1963 et seq.

As cationic dyestuffs to be used in the process of the present invention, those of the series of the azo, azomethine, methine, anthraquinone, nitro, diand triphenylmethane, phenazine, oxazine, thiazine, xanthene and quinophthalone dyestuffs may be employed. Such cationic dyestuffs are disclosed in, for example, Color lndex, 2d Ed., 1956, Vol. 1, pp. 1617-1653; 1963 Supplement, pp. Sl49-Sl77; and Additions and Amendments, No. 1, Sept. 1963 et seq.

The alkaline agents to be added to the dyebaths according to the invention may be used in the quantities generally applied in practice in the dyeing with reactive dyestuffs. The content of alkali in the baths should be so high as to allow adjustment of the pl-l-value to a value in the range of from 9 to 12 and maintaining it during the fixation of the reactive dyestuffs. As alkalis, inorganic compounds having an alkaline action such as potassium carbonate, sodium bicarbonate, sodium triphosphate, sodium diphosphate, sodium hydroxide, sodium silicates, the corresponding potassium compounds or mixtures of these alkaline compounds, but preferably sodium hydroxide solution, are suitably used.

As free acids which are required in the process of the invention for establishing the acid fixing conditions for the dispersion and cationic dyestuffs, there may be used mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acid, or organic acids such, for example as acetic acid or formic acid. Mixtures of these acids may also be used.

However, acetic acid is used preferably. The quantity of free acids to be added to the dyebaths after fixation of the reactive dyestuffs depends in the first instance on the alkali content of the bath and therewith indirectly on the total quantity of reactive dyestuff used, which in turn is dependent on the mixing ratio of the portions of cellulose, polyacrylonitrile and polyester fibers in the textile materials to be dyed.

As non-ionic dispersing agents, there may be used according to the invention either oxethylation products which are derived from fatty acid derivatives such as the fatty amines, fatty acid amides or fat alcohols, the oxethylation products of the fat alcohols being preferred, for example the addition products of 1 mol of stearyl alcohol and 25 moles of ethylene oxide or of 1 mol of oleyl alcohol and 22.5 mols of ethylene oxide, or higher polyglycols having a molecular weight in the range of from 1,500 to 6,000, or mixtures of these products. A mixture of the reaction product of 1 mol of stearyl alcohol and 25 mols of ethylene oxide, and polyglycol having a molecular weight of 6,000, in a mixing ratio of 1:1 to 8:1, preferably 4:1, is preferably used.

As carriers which may be used simultaneously, there may be mentioned the auxiliary agents well known in the dyeing of polyester fibers, for example phenylphenol, p-phenylphenol, benzoic acid alkyl esters and salicylic acid alkyl esters.

Furthermore, the dyebaths may additionally contain the usual electrolytes, wetting or dispersing agents.

The textile material to be dyed according to the process of the present invention and which consists of mixtures of native or regenerated cellulose fibers and fibrous materials of polyacrylonitrile and linear polyesters, preferably polyethylene glycol terephthalate, may have the most various forms, for example the form of flocks, slivers, yarns, fabrics or knit fabrics.

The following Examples illustrate the invention.

EXAMPLE 1:

A mixed fabric consisting of cellulose staple fibers and polyacrylonitrile and polyester fibers in a mixing ratio of 33 33 33 was treated, at a goods to liquor ratio of l 15, for 30 minutes, on a high temperature beam dyeing apparatus, at 60 C, with a bath containing, per liter water, 0.7 g of the reactive dyestuff of the formula (U.S. Pat. No. 3,372,170) and 0.35 g of the dispersion dyestuff of the formula SOZH NH; O OH I /ll\ y Br 1 l I OH O NH:

(French Pat. No. 1,597,864)

The dyebath was heated to C and the fabric was left for 1 hour at this temperature. The dyed fabric was then rinsed and soaped, rinsed again and dried.

fabric were well dyedtone-intone. I

' EXAMPLE 2:

CHa-C O-NH OH ratus at 60 C with a bath which contained, per liter of water, 0.84 g of the reactive dyestuff of the formula (French Pat. No. 1,411,772)

10 0. 84 g of the reactive dyestuff of the formula A textile material as that described in Example 1 was dyed in a manner analogous to that of said Example,

but using as dyestuffs 0.7 g of the reactive dyestuff of the formula SOaH V s 0,0H20H20s0=H l lilH- (U.S. Pat. No. 3,372,170) t g of the dispersion dyestuff of the fomiula 0N /CHzCHr-CO--OCH3 n... QH :Q ".9 91

(Belgian Pat. No. 636,010)

and 0.7 g of the cationic dyestuff of the formula on Cllr- \N -01]; inn-011i BQ f CIh-CHr-CN 9 1...... a a,.. us. Pat. No. 3,332,930)

A tri-color dyeing was obtained on the mixed fabric whose cellulose fiber portion showed a blue 'shade, the polyester fiber portion a red shade and the polyacrylonitrile portion an orange shade.

EXAMPLE 3:

A mixture of polyester, polyacrylonitrile and staple fibers, whose mixing ratio was 33 33 33, inform of (U.S. Pat. No. 3,008,950)

0.77 g of the dispersion dyestuff of the formula CH2CH2-- C 0 O CH:

(Belgian Pat. No. 636,010)

and 0.42 g of the dispersion dyestuff of the formula (German Pat. No. 1,049,821)

in commercial form and composition. The bath additionally contained, per liter of water,

2.0 ml of sodium hydroxide solution of 38 Be, 50.0 g of sodium sulfate,

0.4 g of the reaction product of 1 mol of steary] alcohol and 25 mols of ethylene oxide, and

0.1 g of a polyglycol having a molecular weight of Then, there were added to the dyebath, per'liter of the bath described above,

5.0 ml of acetic acid, 0.32 g of the cationic dyestuff of the formula yarn on cheeses, was dyed at a goods to liquor ratio of l:l5 for 30 minutes in u'high temperature dyeing appa- (Color Index Basic Red 18) and 0.035 g of the cationic dyestuff of the-formula CHz-CH; so

The aforesaid dyestuff may be synthesized according to the process described in U.S. Pat. No. 3,332,930 by coupling diamtizcd 3-methyl-4-aminobenzimidazole with N-ethyl-N-cyanoethyl-anilinc and quaternizing the product so obtained by heating it with dimethyl sulfate.

The dyebath was heated to 125 C and the yarn on the cheeses was left for 1 hour at this temperature. The dyeing was then rinsed, soaped, rinsed again and dried.

A red dyeing was obtained in which the polyester, polyacrylonitrile and staple fiber portions of the mixed yarn were well dyed tone-in-tone.

We claim:

l. A process for exhaust dyeing from a single bath a fibrous material containing a mixture of cellulose fibers, linear polyester fibers and polyacrylonitrile fibers with a reactive dyestuff having at least one vinylsulfone reactive group or one group that forms a vinylsulfone reactive group in alkaline medium, with a disperse dyestuff and with a basic dyestuff, which comprises heating said material at a temperature between about C. and about 80C. in an aqueous dyebath that contains said reactive dyestuff, said disperse dyestuff, a nonionic dispersing agent and an alkaline agent to adjust the pH of said dyebath to between about 9 and about 12 until said reactive dyestuff is fixed on the cellulose fibers, adding to said dyebath said basic dyestuff and a free organic acid or inorganic acid to adjust the pH of said dyebath to between about 3.5 and about 6, and heating said material in said dyebath at a temperature between about 95C. and about 130C. until said disperse dyestuff is fixed on the polyester fibers and said basic dyestuff is fixed on the polyacrylonitrile fibers.

2. A process according to claim 1 wherein said cellulose fibers are dyed at a temperature between about 40C. and about 60C.

3. A process according to claim 1 wherein said polyester fibers and said polyacrylonitrile fibers are dyed at a pH between about 4.5 and about 5.5.

4. A process according to claim 1 wherein a carrier is added to the alkaline bath.

5. A process according to claim 1 wherein a carrier is added to the acid bath.

6. A process according to claim 1 wherein said nonionic dispersing agent is an oxethylation product of a fatty amine, fatty amide or fatty alcohol or a polyglycol of average molecular weight between about 1,500 and about 6,000.

7. A process according to claim 1 wherein said reactive dyestuff is an anthraquinone, an azo or a phthalocyanine dyestuff.

8. A process according to claim 1 wherein said group that forms a vinylsulfone reactive group in alkaline medium is a sulfuric acid ester or a thiosulfuric acid ester of a B-hydroxy-ethyl-sulfone group.

9. A process according to claim 1 wherein said disperse dyestuff is an azo or an anthraquinone dyestuff.

10. A process according to claim 1 wherein said basic dyestuff is an azo, azomethine, methine, anthraquinone, nitro, diphenylmethane, triphenylmethane, phenazine, oxazine, thiazine, xanthene or quinophthalone dyestuff.

. 11. A process according to claim 1 wherein said alkaline agent is sodium or potassium hydroxide, carbonate, bicarbonate, diphosphate, triphosphate or silicate.

12. A process according to claim 1 wherein said free organic or inorganic acid is hydrochloric, sulfuric, phosphoric, acetic or formic acid. 

2. A process according to claim 1 wherein said cellulose fibers are dyed at a temperature between about 40*C. and about 60*C.
 3. A process according to claim 1 wherein said polyester fibers and said polyacrylonitrile fibers are dyed at a pH between about 4.5 and about 5.5.
 4. A process according to claim 1 wherein a carrier is added to the alkaline bath.
 5. A process according to claim 1 wherein a carrier is added to the acid bath.
 6. A process according to claim 1 wherein said non-ionic dispersing agent is an oxethylation product of a fatty amine, fatty amide or fatty alcohol or a polyglycol of average molecular weight between about 1,500 and about 6,000.
 7. A process according to claim 1 wherein said reactive dyestuff is an anthraquinone, an azo or a phthalocyanine dyestuff.
 8. A process according to claim 1 wherein said group that forms a vinylsulfone reactive group in alkaline medium is a sulfuric acid ester or a thiosulfuric acid ester of a Beta -hydroxy-ethyl-sulfone group.
 9. A process according to claim 1 wherein said disperse dyestuff is an azo or an anthraquinone dyestuff.
 10. A process according to claim 1 wherein said basic dyestuff is an azo, azomethine, methine, anthraquinone, nitro, diphenylmethane, triphenylmethane, phenazine, oxazine, thiazine, xanthene or quinophthalone dyestuff.
 11. A process according to claim 1 wherein said alkaline aGent is sodium or potassium hydroxide, carbonate, bicarbonate, diphosphate, triphosphate or silicate.
 12. A process according to claim 1 wherein said free organic or inorganic acid is hydrochloric, sulfuric, phosphoric, acetic or formic acid. 